Printing paste for textile fabric



United-Stat s .Path psentemiiiftii 1 i l i i Y 2 p 980,487 in water. They require an alcohol for putting them into PRlNTmG PASTE O TEXTILEFABRIC solution, and the OllfiS commonly usedill commercial Robert Johnson Summeril] i am or to processes .with these coloring agents are the lower mono- E. I. du Pont devNemoursiand companywflglgton alkyl ethers (methyl to buty l) of ethylene glycol and o f I DeL, a corporation of Delaware j I v i No Drawing. "Filed 'July'25,*1958,' ser. No. 750,863 m m i l P rr methylene 9 a b and Claims. I s .copper-phthalocyan1ne precursors W111 be selected for all v i I 1 a a further discussion which follows, but'it will be understood Tthlsvmventlm} 1 W .n 1. m y lm that my invention is not limited to these specific agents. P s d Prmtmg' P which P9 9 b 10 Now, the attempt to apply the aforementioned wateruphthalocyamne precurfmls m dP am b fi l in-oil printing technique to copper phthalocyanine preybw nfl l ve Q on the b EQ-P QdU m. cursor has been disappointingly thwarted by the fact that li n x emely -t rtan? L theCarbito1 employed for dissolving the precursor has In f n-i x i b l ih P 3 2 2 H9? v i -"3 a stron'g'tendency to break up the water in-oil emulsion, dyes f Practicall Problems anse Such F of 15 with the result that the printing paste either cannottbe the P P se! Sharpness of defimnon of thei I prepared at all or is so unstable as not't o'be useable in printed pattern, and fastnessto crocking. In recent years ordinary practice 3- hQ .P m l 'f m i' l i dyes ,3 e It is accordingly anobject of this invention to provide developed which overcomes the above probl a a a novel water-in-oil emulsion printing paste for phthalo satisfactory degrfm rin i l Q F F FE UR 20 cyanine precursors which has s'ufiiciently good stability w method reslde 111 the 9 w fi jf i r n 9P "for'p'rac'tical'i3urpose's." It'is a furtherobj'ect of'this inveni form we body of the pnntlngvpastefln the -1 of n tion to provide novel printing paste formulations of alkali-permeable alkydjresinftog'ether "with pine oilas :phtfialopyanine precursors which impart cxcegdingly r i s agent f P d i Said: enmlsliofii 3 1 l b 'ghfis'hades-to-the printed textile and which give prints i i g li imfi vfi after y if t 9i i o' f exceptionally good light-fastness, wash fastn'ess, and l g e m rfi k b ,.f. 4,by lg F ii; resistanceto crocking-.- Other objects and achievements i lmprlnted Color, and h i b 9 m h fabric to, m of'this invention will appear as the description proceeds.

action of an oxidizing l fllii Primed P i v m- I Now, I find- I that the above-mentioned" destructive Bylalkali f g? fs 'v ire i --vtendency-of the Carbitol on the water-in-oil emulsion Which is a y permeated P 115 91? byfibw r 30.lcan be iovercome by incorporating into the emulsion,'prior alkali reducmg l nse vm' prm't p ast 1 to, mryjor he Carbitol-precursor solution, a stabilizing resin'is p r b y am fls y f s iiwh h, Soluble iinifidsi't'ibri"@h riihgboth ethyl eermids and an ali- 1n aqueous me r d m s ns t 2 h p hatic alcohol are to'8 'c-afdms whichissparingly'soluble 5 diethylene glycol. To typify commercial practice, the

advantage of using such a resin is that whil acting as a {in watcrgpqtpyer 2% by Wight). Aspracfioal exampks bonding agent during the+printing step, the resin will be 35 jofjtphglattef yb -f d methylamyl a'lcbh'ol 44 1133 removed by-t h e heated caustlc solution ,on the textile as 1-; y fit bpzx'jmefhy pfi bp zthylflfiffibl h at it passes through the steaming step, 3 ,;anol and heptanol-3. In recent years, a n w c s of lQ f g PEPE? P P? The quantity "of the stabilizing composition required devel p d, f i fm n r ly, PQ j QmmF for satisfaotory' re's'ul-tsis not very greatl It may vary P JEQ Q Y Q P Q U S h? QQPP QI 1 P9P?" ,iI'QHljDJS. to;;0.3. 0 part of ethyl cellulose and from 0.5 ,mercral representative 0f w leh .8, QPPQ ll i l lt to 2. O -parts of the sparinglysoluble alcohol 100 parts precursor V I I I o f the ultimate printing paste. The two agents are pref- The Precursor for a metal-phthalocyamne I ly dissolved in xylene (from 0.5 to 4.0 parts per IQO e ned}? an lcqhdaqhklq 99191 1 9 999 19 @011- "p is or printing-paste); 'and are-"stirred-into tlie *oi ly ta gm 'm h A p h pp t e r q w q 45 phase'together'with a" solution of"the-alkali=permeable .zwhich lias no'itlnctonalrqualities miitself, buttwhich upon alkydre'sin in xylene, prior to entry of the Water which 1y? h I heating or uponcbeing treatedwithfsreducing agents' yields gt -j 'ffi precedes. h i i f f he r s e s e w mee. ath -ser e?anPF i l solution: I cyamne precursor, the compound maybe: expressed by igengral my 'preferred'pmcedmem b h the empirical formula GuTGgHgNJNI-IP wherein tlie 'i5 a is 5 six units in parenthesesgmay be looked uppn as phthalo l f 1 gni trile units, theprecursors being in factcapablepf being (a) ALKYD RESIN toi'nied-by reacting o6molesof plitlial'onitrileiw h,1;,.m0le An alkali permeable alkyd resin, usually in the I t pr qsa tin an inert or a QQ lt, rated With form of a xylene solution, 'is'rnixed-with pi'n'ebiI -and w p. F h r a ilg n ilfl ipQ l i fiqjhi then 'an--aqueous solutionof diammoniumphosphate' is m d of u c -m y b found s fit lis N i y, 'jaddqdfa's the mass is vigorously agitated to prepare the v claimed in US. Patent No. 2,581

- resin now on the market made,-byausirr i l ors are gener A 2% hthali g anhydride and 37% n sed. Quit-he educln'g bathand I Now, because the phthalocy I wally developed by -treatment with l-:i gredients inl-this. step rings U balance being theconve 10 1" 01 h ,dr icalcoho; such r .heatirig, it' would'appear off handh xcept foromittii'ig 1 i 'i "1 i ffthe oxidizing step, the aforementioned watr-iri=oil"emulgene ous paste is obtained. 7

3 t (b) STABILIZER SOLUTION This is prepared by mixing together ethyl cellulose, methylamyl alcohol and xylene in the proportions indicated above. A clear solution is obtained.

() HYDROCARBON OIL' Amsco Varsol Hydrocarbons N 0. 46, No. 2,

Percent Percent Paraffinic 58 31. 0 Naphthenic.. 23 34. 5 Aromatic 19 34. 5

(d) WATER-IN-OIL EMULSION (SO-CALLED CLEAR) The aforegoing three compositions are put together in the following proportions:

Parts Alkyd resin concentrate (a) 2.5 to 7.5 Stabilizer solution (b) 1,5 to 2.5

Hydrocarbon oil (c) 26 to 45 Total 30 055 The mixture is stirred in a homogenizer typernixer and water is fed in gradually until an emulsion of desired consistency. has been obtained. Customarily, the water added will be in the following proportion:

. Parts Mixture of (a), (b) and (c) 30m 55 Water 48 to 14 Total clear 78 to 69 (e) COLORING OLUTION The selected precursor is dissolved in the chosen solwater-in-oil emulsion. It is significant that unless the ethyl cellulose and methylamyl alcohol are present as pointed out above the print paste composition will not be stable and will therefore not be useful in a commercial printing process. Experiments have proven that in the absence of ethyl cellulose the printing process is inoperable and in the absence of the methylamyl alcohol the stability of the paste is much inferior to the print paste of this invention.

It a vat dye is to be added for shading purposes, it is generally incorporated in the form of an aqueous paste into the final printing paste obtained in step (f). Customarily, jade green (Q1. 1101) or a violet vat dye is employed for this purpose, but other vat dyes may be used if desired. The amount of vat dye used for shading purposes is usually small, in the order of less than 1 percent of the final printing paste (about percent); howevenlarger amounts of vat dyes may readily be used.

(g) PRINTING PROCEDURE oxidation bath such as sodium dichromate and acetic acid' solution, after which'the fabric is soaped and dried in the conventional manner.

Without limiting this invention, the following examples are given to illustrate my preferred mode of operation. Parts mentioned are by weight.

Example 1 (A) AIJKYD? RESIN EMULSION A mixture of 60 parts of a 60% by weight solution of a cottonseed oil modified alkyd resin in xylene and 12 parts of pine oil were prepared by mixing the ingredivent (usually Carbitol) in the following proportionsz Parts Precursor 0.04 to 20 Solvent 99.96 to .80

Tot al '100.00,f.100

(f) FINAL PRINTING PASTE To the emulsionobtained in step (d), while still in the homogenizer, the coloring solution (e) is added in the following proportion:

Stirring in thehomogenizer is continued until a homo- The quantityofcolori ng agent added in step (1) and -the proportionof phthalocyanine precursorin'step (e) are generally correlated so that; the. quantity of fCar- 20% by weight Thus, with a coloring cornposition-contaihing over 99% byweight of the solvent, any q'uantity thereof from 22-to 31 p'arts when usedin step '(f) will 5 parts of ethytlenefid velopment of color). y

f tain homogenization.

ents. Then,'a solution of 3 parts of diammonium phosphate in 25 parts of water was added and homogenized into the alkyd resin solution resulting in a white viscous paste.

is ETHYL CELLULQSEALCOHOL SOLUTION A solution of 8.parts of ethyl cellulose (type N, grade 50) and 22.5 parts of methylamyl alcohol Ha)2- C 2 3) was. dissolved in 55 parts of xylene.

(C AND D) EMULSION CLEAR A mixture of parts of A, 25 parts of B and 320 parts of hydrocarbon solvent (a commercial mixture of 23% naphthenic, 58% paraffinic and 19% aromatic hydrocarbons, B.R. l05-300 'C.) was prepared and then 500 partsof Water slowly added as the mixture was agitated with a homogenizer. -A uniform whitefiemulsion was obtained.

H (I?) PBECURSOR COMPOSITION 20 parts of copper phthalocyanine L precursor (Example.3.of U;S'.P.12,772,283) .was dissolved in: 2 20 parts.

of themonoethyl ether of diethylene glycol containing iamine (to prevent .prematureldex (EYiRINTIN i solution, sweeten tofl 1 and itw added to 755 parts. ofjthe' clearwith vigorous mixing to obprolonged storage or when used on textile printing machines.

(G) PRINTING PROCESS Bleached cotton fabric was passed through a textile roller printing machine which furnished the above print paste composition by a doctor blade to the engraved roll. The printed cloth was dried by passing through an oven at 160 F. Then the print was developed by passing the printed textile through a reducing pad bath containing caustic and sodium hydrosulfite and then it was passed through an air-free steam atmosphere. The print was then rinsed, washed and dried in the conventional mannet.

The final print was a bright blue which shows excellent light and wash-fastness.

When the printing paste of this example was prepared as above but without methylamyl alcohol, the printing paste stability immediately after preparation was inferior to that obtained above, and it became progressively worse on daily inspection.

Example 2 Example 1 was repeated except that the printing paste was shaded with a conventional vat dye. This was done by incorporating 0.67 partof an 11% paste of dimethoxydibenzanthrone to the clear after the precursor solution has been added. The resulting print paste was stable on the printing machine and was used to print cotton fabric as in Example 1, except that after the steaming operation the fabric was, rinsed in cold water and the vat dye was oxidized by passing the printed fabric through a bath of sodium bichromate and acetic acid.

The finished fabric was a bright print of a greenish blue which showed excellent sharpness of print and had excellent light and wash-fastness.

It will be understood that the details of procedure may be varied within the skill of those engaged in this art.

I claim as my invention:

1. The process of preparing a stable Water-in-oil type printing paste for printing textile fabric with a phthalocyanine precursor, which comprises forming an emulsion of water in oil by the aid of an emulsifier comprising pine oil and an alkali-permeable alkyd resin, further including in said emulsion a stabilizer comprising ethyl cellulose and a sparingly soluble aliphatic alcohol of 6 to 8 C-atoms, and then incorporating into said emulsion a solution of a phthalocyanine precursor in a lower monoalkyl ether of diethylene glycol.

2. A stable printing composition for printing textile fabric with a phthalocyanine precursor, said composition comprising a water-in-oil emulsion containing per 100 parts of total weight, from 2.5 to 7.5 parts of an emulsifier comprising pine oil and an alkali permeable alkyd resin, from 1.5 to 2.5 parts of a stabilizer comprising ethyl cellulose and a sparingly soluble aliphatic alcohol of 6 to 8 C-atoms, from 22 to 31 parts of said phthalocyanine precursor dissolved in a lower monoalkyl ether of diethylene glycol, and from 48 to 14 parts of water, said oil making up the difference and being composed essentially of a mixture of aliphatic, cycloaliphatic and aromatic hydrocarbons which are liquid in the range beween room temperature and 105 C.

3. A process of printing textile fabric, which comprises applying thereto a stable printing paste as defined in claim 2, drying the printed fabric, padding the same in an aqueous reducing bath comprising alkaline hydrosulfite and steaming the padded fabric to develop the printed pattern. i

4. A stable printing composition as in claim 2, said composition comprising further a vat dye in quantity not exceeding 1% by weightof the entire printing composition.

5. A process of printing cotton fabric, which comprises applying thereto a stable printing paste as defined in claim 4, drying the printed fabric, padding the same in an aqueous reducing bath comprising alkaline hydrosulfite, steaming the padded fabric, and passing the same through an aqueous oxidizing bath to develop the final printed pattern.

6. A printing composition for textile fabric comprising a water-in-oil emulsion containing, per parts of total weight, from 2.5 to 7.5 parts of an emulsifier comprising pine oil and a cotton-seed-oil modified alkyd resin, from 1.5 to 2.5 parts of a stabilizer comprising ethyl cellulose and a sparingly soluble aliphatic alcohol of 6 to 8 C-atoms, from 22 to 31 parts of copper phthalocyanine precursor dissolved in a lower monoalkyl ether of diethylene glycol, and from 48 to 14 parts of water, said oil making up the difference and being composed essentially of a mixture of aliphatic, cycloaliphatic and aromatic hydrocarbons which are liquid in the range between room temperature and C.

References Cited in the file of this patent UNITED STATES PATENTS 2,288,261 Abrams June 30, 1942 2,332,121 Trowell Oct. 19, 1943 2,681,348 Brooks June 15, 1954 2,772,283 Stevenson Nov. 27, 1956 2,772,284 Barnhart et a1. Nov. 27, 1956 2,878,096 Wood et a1 Mar. 17, 1959 OTHER REFERENCES Schwartz et 211.: Surface Active Agents, vol. 1, 1949, pp. 214-217, Interscience Publishers, Inc., New York. 

2. A STABLE PRINTING COMPOSITION FOR PRINTING TEXTILE FABRIC WITH A PHTHALOCYANINE PRECURSOR, SAID COMPOSITION COMPRISING A WATER-IN-OIL EMULSION CONTAINING PER 100 PARTS OF TOTAL WEIGHT, FROM 2.5 TO 7.5 PARTS OF AN EMULSIFIER COMPRISING PINE OIL AND AN ALKALI PERMEABLE ALKYD RESIN, FROM 1.5 TO 2.5 PARTS OF A STABILIZER COMPRISING ETHYL CELLULOSE AND A SPARINGLY SOLUBLE ALIPHATIC ALCOHOL OF 6 TO 8 C-ATOMS, FROM 22 TO 31 PARTS OF SAID PHTHALOCYANINE PRECURSOR DISSOLVED IN A LOWER MONOALKYL ETHER OF DIETHYLENE GLYCOL, AND FROM 48 TO 14 PARTS OF WATER, SAID OIL MAKING UP THE DIFFERENCE AND BEING COMPOSED ESSENTIALLY OF A MIXTURE OF ALIPHATIC, CYCLOALIPHATIC AND AROMATIC HYDROCARBONS WHICH ARE LIQUID IN THE RANGE BETWEEN ROOM TEMPERATURE AND 105*C. 